ES2205777T3 - IMPROVED PROCEDURE FOR THE PRODUCTION OF A DIHYDROXIBENCEN AND DICARBINOL FROM DISOPROPILBENZENE. - Google Patents

Abstract

A method of manufacturing dihydroxybenzene and dicarbinol from diisopropylbenzene, comprising: a) oxidizing diisopropylbenzene (DIPB) in the presence of a basic catalyst to obtain an oxidized product comprising diisopropylbenzene dihydroperoxide (DHP), hydroxyhydroperoxide diisopropylbenzene (hydroxybenzene) of acetylisopropylbenzene (KHP) and one or more members selected from the group consisting of diisopropylbenzene monohydroperoxide (MHP), isopropylbenzenemononocarbinol (MCL), diisopropylbenzenedicarbinol (DCL), acetylisopropylbenzenemononocarbinol (KCL) and organic peroxides; b) feed the oxidized product of step a), a solution of caustic soda and an organic solvent to a first Karr column; c) generate two streams from the first Karr column of stage b), the first extruction stream with caustic soda DHP, HHP and KHP being extracted in a countercurrent operation, and comprising the second excision stream with caustic soda, comprising one or more members selected from the group consisting of MHP, MCL, DCL, KCL, other organic peroxides, DIPB and the organic solvent of step b); d) feeding the first excretion stream with caustic soda from step c), an organic solvent cooled to a temperature between 10 and 30 ° C and an alkaline solution to a second Karr column; e) generating two streams from the second Karr column, the first cold extraction stream comprising a cold organic solvent extract comprising HHP and KHP and the second caustic soda cold extraction stream enriched in DHP; f) feeding an organic solvent having a temperature between 40 and 85 ° C and the DHP-enriched caustic soda from step e) to a third Karr column; g) generating two streams from the third Karr column, the first hot extraction stream comprising a solution in hot organic solvent comprising high purity DHP, and the second poor caustic soda hot extraction stream having low levels of hydroperoxides not extracted; h) concentrate the solution in hot organic solvent of step g) and feed the concentrate to a continuous dissociation reactor in which DHP is dissociated in the presence of an acid catalyst to produce a solution comprising the corresponding dihydroxybenzene and acetone; and i) decomposing the HHP present in the first cold extraction stream of step e) by treatment with an aqueous alkaline solution under atmospheric pressure and aqueous conditions to obtain the corresponding dicarbinol.

Description

Improved procedure for the production of a dihydroxybenzene and dicarbinol from diisopropylbenzene.

Field of the Invention

The present invention relates to a Enhanced procedure for continuous simultaneous production of dihydroxybenzene (DHB) and diisopropylbenzenedicarbinol (DCL) from of diisopropylbenzene. More specifically, this procedure It includes the steps of: oxidizing diisopropylbenzene to obtain a oxidized product comprising, among other things, dihydroperoxide of diisopropylbenzene (DHP) and hydroxyhydroperoxide of diisopropylbenzene (HHP); extract DHP and HHP from the oxidized product in an aqueous solution of caustic soda using an operation in a Karr's column; continuously and simultaneously isolate HHP and DHP in separate fractions of the caustic soda solution using hot and cold extractions with methyl isobutyl ketone (MIBK) in the Karr's column; produce dihydroxybenzene by dissociation of the fraction of the DHP extract in the presence of a catalyst acid; and produce dicarbinol by breaking down the low HHP fraction atmospheric conditions using an alkaline aqueous solution.

Background of the invention

It is known in the art that hydroperoxides, such as diisopropylbenzene dihydroperoxide (DHP), diisopropylbenzene monohydroxyperoxide (MHP) e diisopropylbenzene hydroxyhydroperoxide (HHP), can be produced oxidizing diisopropylbenzenes with molecular oxygen in the presence or absence of basic catalysts. Oxidation and production of diisopropylbenzene dihydroperoxide from diisopropylbenzenes in the presence of a strong base, such as sodium hydroxide, are described, for example, in British Patent No. 727,498 and U.S. Pat. 3,953,521. These patents describe that m- and dihydroperoxides can be continuously isolated p-diisopropylbenzene from the mixture of oxidation of diisopropylbenzene by soda exraction caustic, and that the continuous oxidation of diisopropylbenzenes for Dihydroperoxide production can be achieved by keeping the pH at an interval between 8 and 11 and the temperature at approximately 85-95 ° C in the oxidation reactor. The patent British No. 727,498, as well as US Pat. No. 2,856,432, also describes that the dihydroperoxides (DHP) present in the diisopropylbenzene oxidation mixture can be separated effectively through caustic soda solutions to 4-8% by weight. In addition to dihydroperoxide (DHP), part of the hydroxyhydroperoxide (HHP) present in the material Oxidation is also extracted in the caustic soda solution.

U.S. Pat. No. 4,237,319 also describes a method for the discontinuous production of dihydroperoxide m-diisopropylbenzene (m-DHP) oxidizing m-diisopropylbenzene under conditions alkaline

Japanese Patent No. 9,143,112 (extract) describes the discontinuous production of dihydroxybenzene and dicarbinol from the oxidation of diisopropylbenzene followed by the Extraction with sodium hydroxide.

The extraction of DHP in the soda solution Caustic, which is described in the prior art, may be followed by the isolation of DHP for the production of a phenol dihydroxylated, such as resorcinol or hydroquinone, in various ways. Of these methods, a preferred method in the art is to extract the DHP of the caustic soda solution in an organic solvent, preferably MIBK. Using this solvent, a temperature of 70-80ºC and contact times of 5-10 minutes, it is possible to extract a high proportion of DHP in MIBK with negligible losses due to decomposition. The British Patent No. 921,557 describes that m-DHP present in the aqueous solution of caustic soda is extracted by the MIBK solvent at 75 ° C. To improve extraction efficiency, U.S. Patent No. 3,932,528 describes that adding ammonia approximately 1% in an 8% aqueous solution of caustic soda Containing 12.3% DHP, the MIBK solvent is more effective at 60 ° C for the extraction of DHP through three phases of contact in countercurrent

U.S. Pat. No. 4,059,637 describes a method by which DHP present in the soda solution is extracted Caustic using MIBK solvent in a type extraction mixer-settler in countercurrent in four phases The caustic soda solution containing DHP used in the mixer-settler extraction is about previously with MIBK, at a temperature of less than 30 ° C, to remove oxidation by-products that have the group 2-hydroxy-2-propyl, such as diisopropylbenzene hydroxyhydroperoxide (HHP) and diisopropylbenzenecarbinol (DCL). It is presented that the content of HHP of the caustic soda solution containing DHP before feed the extraction with mixer-settler It is approximately 4.2%. After extraction, it is presented that The purity of DHP in the MIBK solution is 93%.

Several patents describe different acid type catalysts and temperatures to obtain a phenol dihydroxylated, such as resorcinol or hydroquinone, from DHP by dissociation. For example, British Patent No. 743,736 describes sulfuric acid as the catalyst for dissociation of m-DHP in the presence of a low MIBK solvent reflux conditions. With a residence time between approximately 7.5-10 minutes and a catalyst of H 2 SO 4 at 0.2% by weight, 99.6% of DHP is decomposed. The British Patent No. 819,450 describes a trioxide catalyst of sulfur for dissociation of m-DHP; It is presented that sulfur trioxide causes a dissociation reaction much more faster than the corresponding amount of sulfuric acid. The m-DHP decomposition is carried out continuously in two reactors connected in series, using MIBK and acetone as the solvents used in the operation of dissociation. Canadian Patent No. 586,534 also describes the use of a sulfur trioxide catalyst to dissociate m-DHP in the presence of 0.3% water by weight in the dissociation reaction. U.S. Pat. No. 3,923,908 describes a procedure to dissociate dihydroperoxides from diisopropylbenzene in the presence of impurities such as isopropylphenyl dimethylcarbinol (MCL), hydroxyhydroperoxide diisopropylbenzene (HHP) and diisopropylbenzenedicarbonol (DCL) using a sulfur trioxide catalyst and a solvent.

To effectively use the byproduct Diisopropylbenzene Hydroxyhydroperoxide (HHP) Application Japanese Patent 95-304027 and the Patent Application Japanese No. 95-301055 describe a method by which a solution in MIBK containing HHP is reduced by hydrogen in the presence of a palladium-alumina catalyst (a material that has 1% by weight of metallic palladium) in a autoclave equipped with a stirrer, at a hydrogen pressure of 6 atmospheres and a reaction temperature of 90 ° C, to obtain diisopropylbenzenedicarbinol (DCL). Although this method produces DCL to Starting with HHP, the safety of this procedure is questionable, since it involves handling hydrogen at high pressure in the presence of a Highly volatile solvent (MIBK) at high temperatures.

An important aspect recognized in the art to produce high purity dihydroxylated phenol by hydroxyperoxidation technology is to prepare a diet High purity dissociation (DHP) from the mixture of diisopropylbenzene oxidation. Although DHP occurs in the DIPBP oxidation, it may not be easy to completely remove DHP of the oxidation mixture for use in the dissociation step of the hydroperoxidation procedure. In a first standard stage of DHP separation of the oxidized product, is typically performed Extraction with caustic soda using a 4% or 8% NaOH solution. During this extraction, DHP, as well as other impurities present in the oxidized product, such as HHP, hydroperoxide Acetylisopropylbenzene (KHP) and / or MHP are extracted. When one is used 8% NaOH solution, it is known that approximately 90-95% of the HHP and KHP present in the mixture of oxidation is extracted in the caustic soda solution, along with approximately 1-2% of MHP. The MHP present in the Caustic soda solution is extracted again with a solvent of DIPB The solution comprising the DIPB, MHP extracted and others oxidation impurities can be recycled to the oxidation reaction and undergo oxidation. However, this extraction of DIPB does not have much effect on the removal of other impurities such as HHP and KHP of the caustic soda extract solution. To remove the HHP of the caustic soda solution, typically a solvent extraction of MIBK at a low temperature. In spite of this operation, the concentration of HHP in the soda solution Caustic before extraction with final MIBK can still be relatively high and therefore it has been found that this method it is a difficult route to produce DHP of very high purity for the dissociation. None of the patents or other literature in the art suggests or describes what happens to impurities such as KHP present in caustic soda extract. If the procedures or the extraction methods are not effective, then it is expected that impurities of the hydroperoxidation process interfere with the isolation of a DHP of very high purity necessary for a highly efficient dissociation operation. Nothing of the technique teaches or suggests a procedure whereby, in a continuous operation, DHP of very high purity can be produced from oxidation materials of diisopropylbenzene.

In an attempt to develop a DHP material from high purity, US Pat. No. 4,059,637 describes a method in which uses four type extractors mixer-settler. The caustic soda solution containing DHP used in the '637 patent contained DHP and HHP in a ratio of approximately 95.8: 4.2, even after it perform the extraction with MIBK at 20 ° C on the solution. From According to this patent, this extraction with cold MIBK from the Extraction with caustic soda was performed separately as a discontinuous procedure instead of integrating with the operation of extraction in the mixer-settler. East procedure produced a product containing low purity DHP for the dissociation reaction.

Thus, the techniques used in the specialty for prepare a high purity DHP from oxidation materials of DIPB have disadvantages. No single procedure describes completely a continuous method to obtain a high purity DHP from the oxidized product, while identifying and characterizing the nature of impurities extracted in soda extractions Caustic and MIBK. In addition, the methods described in the specialty to prepare DCL from oxidation materials of DIPB give Place to security problems. Therefore, there is still one need for a procedure that provides preparation Safe and effective products such as a DHP feed from High purity to use in the preparation of DHB, as well as DCL.

Summary of the invention

In accordance with the present invention, provides a method of making dihydroxybenzene and dicarbinol at starting from diisopropylbenzene, which comprises: a) oxidizing diisopropylbenzene (DIPB) in the presence of a basic catalyst for obtain an oxidized product comprising dihydroperoxide of diisopropylbenzene (DHP), diisopropylbenzene hydroxyhydroperoxide (HHP), acetylisopropylbenzene hydroperoxide (KHP) and one or more selected members of the group consisting of monohydroperoxide of diisopropylbenzene (MHP), isopropylbenzenemononocarbinol (MCL), diisopropylbenzenedicarbinol (DCL), acetylisopropylbenzenemononocarbinol (KCL) and other peroxides organic; b) feed the oxidized product from step a), a caustic soda solution and an organic solvent to a first Karr's column; c) generate two currents from the first Karr column of stage b), comprising the first stream Extraction with DHP, HHP and KHP caustic soda extracted in a countercurrent operation, and comprising the second current one or more selected members of the caustic soda group consisting of MHP, MCL, DCL, KCL, other organic peroxides, DIPB and the organic solvent of step b); d) feed the first caustic soda extraction stage c), a organic solvent cooled to a temperature between 10 and 30 ° C and an alkaline solution to a second Karr column; and) generate two streams from the second column of Karr, the first cold extraction stream comprising an extract of cold organic solvent comprising HHP and KHP and comprising the second stream of cold extraction caustic soda enriched in DHP; f) feed an organic solvent having a temperature between 40 and 85ºC and the caustic soda enriched in stage DHP e) to a third column of Karr; g) generate two streams from of the third column of Karr, comprising the first stream of hot extraction a solution in hot organic solvent that comprises high purity DHP, and comprising the second stream hot extraction poor caustic soda that has low levels of hydroperoxides not extracted; h) concentrate the solution on hot organic solvent from stage g) and feed the concentrated to a continuous dissociation reactor in which dissociates DHP in the presence of an acid catalyst to produce a solution comprising the corresponding dihydroxybenzene and acetone; and i) decompose the HHP present in the first current of cold extraction of stage e) by treatment with a solution aqueous alkaline under atmospheric pressure and aqueous conditions for Obtain the corresponding dicarbinol.

Preferably, they are continuously performed at minus two successive stages selected from the group consisting of any of steps a) to g).

Alternatively, the oxidation of Diisopropylbenzene is performed using molecular oxygen.

Advantageously, the oxidation stage is performed using a continuous or discontinuous method.

Preferably, said oxidation step is performed at a temperature between approximately 80 ° C and 120 ° C and a pressure between 1.38 and 5.52 bar (20 and 80 psi) and using as the basic catalyst an alkaline solution selected from the group that It consists of sodium carbonate and sodium hydroxide.

Conveniently, the organic solvent of the stage b) is DIPB.

Advantageously, the method also includes the stage to recycle the second excretion stream with caustic soda produced in stage c) to the oxidation stage of stage a).

Preferably, the organic solvent used in stage d) and stage f) is methyl isobutyl ketone (MIBK).

Advantageously, the temperature of the solution inside the second column of Karr is between 10 and 30 ° C.

Conveniently, the temperature of the solution in the third column of Karr is between 40 and 85ºC.

Preferably, the first stream of Extraction with caustic soda from stage c) is fed directly to the cold extraction of stage d), and the second stream of cold extraction of stage e) is fed directly to the hot extraction from stage f).

Advantageously, the concentration of stage h) it is done by feeding the hot organic solvent solution to a vacuum evaporator

Preferably, the temperature of the solution inside the dissociation reactor in step h) is between 60 and 80 ° C

Alternatively, the decomposition stage i) It is performed at a temperature between 90 and 105 ° C.

Conveniently, said first column of Karr, said second column of Karr and said third column of Karr are They work in series.

Preferably, the aqueous alkaline solution of step i) is selected from the group consisting of a solution aqueous sodium sulphite and an aqueous hydroxide solution sodium

Advantageously, the stirring speed in the Karr's first column is between 0.83 and 5.0 Hz (50 and 300 runs per minute), the agitation speed in the second Karr column is between 1.67 and 6.67 Hz (100 and 400 paths per minute) and stirring speed in the third column of Karr is between 1.67 and 6.67 Hz (100 and 400 paths per minute).

Conveniently, the acid catalyst of the stage h) is one or more members selected from the group consisting in sulfuric acid, sulfur trioxide, phosphoric acid, acid hydrochloric, boron trifluoride and acid p-toluenesulfonic.

Alternatively, the acid catalyst is sulfur trioxide.

Advantageously, the method also includes the stage of recovering MIBK from the poor caustic soda current generated in stage g) and the decomposition current in stage i) to recycling.

Conveniently, the organic solvent in the first cold extraction stream is removed before the stage of decomposition of stage i).

Advantageously, the method also includes the stage to determine the composition of one or more selected streams from the group consisting of the oxidized product, the first stream Extraction with caustic soda, the second current of exraction with caustic soda, the first cold extraction stream, the second cold extraction current, the first current of hot extraction, the second hot extraction current and the dissociation product of step h) using analysis of PMR

Conveniently, the current being analyzed is select from the group consisting of the oxidized product, the first Extraction current with caustic soda, the second current of Extraction with caustic soda, the first extraction current cold, the second extraction current cold, the first current hot extraction and the second hot extraction current and the analysis by PMR comprises: a) obtaining a spectrum of PMR to a current; b) determine the integral of a peak that represents each compound in the stream in the PMR spectrum; c) divide the integral of each peak by the number of hydrogens that give rise to each peak to obtain the molar fraction for each compound in the stream; and d) repeat steps a) to c) for each current that It's analized.

Preferably, the current being analyzed is select from the group consisting of the first stream of Extraction with caustic soda and the second current of exraction with caustic soda, and also includes the stage of extracting the solution of caustic soda of the current before performing the analysis by PMR

Alternatively, the current analyzed is the decoupling product and the PMR analysis comprises: a) add a standard internal to the dissociation product; b) obtain a spectrum PMR for the dissociation product / chloride mixture methylene; c) determine the weight of each analyte in the product of dissociation according to the formula:

\ analyte weight = (weight \ of \ internal \ pattern) \ (N_ {s} / N_ {a}) (M_ {a} / M_ {s}) (A_ {a} / A_ {s})

where

N_ {s} = number of protons of the internal standard (2 for methylene chloride)

N_ {a} = number of protons in the analyte for measured structure

M_ {s} = molecular weight of the standard (85 for methylene chloride)

M_ {a} = molecular weight of the analyte

A_ {s} = area of the pattern integral

A_ {a} = area of the analyte integral.

The present invention has found the means previously described providing a new procedure for preparation of a dihydroxylated phenol, such as resorcinol or hydroquinone, from a dissociation feed that It contains high purity DHP while also using effectively the impurity of HHP in the oxidation product of DIPB for the manufacture of dicarbinol. This method includes generally the stages of oxidizing diisopropylbenzenes with oxygen molecular in the presence of a basic catalyst to obtain a oxidation reaction mixture, also referred to herein as "product oxidized ", which comprises, among other things, dihydroperoxide of diisopropylbenzene (DHP) and hydroxyhydroperoxide of diisopropylbenzene (HHP); feed the oxidized product to a Karr column, also called here "column of exraction with caustic soda "; continuously and simultaneously extract DHP and HHP of the oxidized product in a countercurrent operation; generate continuously a solution of caustic soda enriched in DHP / HHP, also called here "rich caustic soda solution", and a recycle stream, recycle stream that can be fed directly back to the oxidation reactor; feed continuously the solution of rich caustic soda to a second Karr column, also called here "MIBK column cold ", for the simultaneous and continuous generation of solution of caustic soda enriched in DHP and the separation of HHP from the DHP-enriched caustic soda solution achieved by performing this extruction operation with MIBK at a low temperature, also here called "cold MIBK excision"; feed continuously the caustic soda solution enriched in DHP at a Karr's third column, also called here "MIBK column hot ", for the continuous generation of a DHP of purity very high to get a MIBK solution, called here "solution of hot MIBK ", to feed a dissociation stage for continuous generation of dihydroxybenzene and continuous generation of a poor caustic soda solution that contains very high levels low hydroperoxides not extracted. Before dissociation, the Hot MIBK solution is preferably concentrated; the concentrate is then fed to a dissociation reactor continuous where DHP dissociates in the presence of a catalyst to produce the corresponding dihydroxylated phenol, such as resorcinol or hydroquinone, and acetone. The HHP present in the MIBK extract cold obtained after the second Karr column extraction is decomposes by treatment with an alkaline aqueous solution under atmospheric and aqueous conditions to obtain dicarbinol correspondent.

Therefore, an objective of the present invention is to provide an improved method for the production of polyphenols, such as resorcinol or hydroquinone, and dicarbinol from diisopropylbenzenes.

A further objective of the present invention is provide a procedure for continuous separation of DHP from DIPB oxidation material and the generation of a feed of oxidation recycling and a stream of caustic soda rich from the Extraction with caustic soda using column operations Karr

A further objective of the present invention is provide a procedure for continuous separation and highly effective impurities such as HHP, KHP, MHP and others oxidation impurities of the caustic soda stream rich in DHP / HHP performing a cold temperature MIBK excision in a Karr column.

Another object of the invention is to provide a procedure for the production of a caustic soda solution enriched in DHP for high temperature MIBK excision in a column of Karr.

Another objective of the present invention is provide a procedure for the continuous production of a very high purity DHP material feed for the stage of dissociation of the hydroperoxidation process by performing MIBK extractions on the caustic soda extract solution using operations on Karr columns.

A further objective of this invention is provide an aqueous, non-hydrogenated, safe, effective procedure and efficient for the conversion of HHP into DCL.

These and other objects of the invention will be evident from the following detailed description of the invention.

Brief description of the drawing

Figure 1 is a schematic flow chart for a preferred embodiment of the process for producing phenol dihydroxylated and dicarbinol from diisopropylbenzene according with the present invention.

Detailed description of the invention

A method for manufacturing is described dihydroxybenzene and dicarbinol from diisopropylbenzene, which it comprises: a) oxidizing diisopropylbenzene with oxygen in the presence of a basic catalyst to obtain a reaction mixture of oxidation or "oxidized product" comprising dihydroperoxide of diisopropylbenzene (DHP), diisopropylbenzene hydroxyhydroperoxide (HHP), acetylisopropylbenzene hydroperoxide (KHP) and one or more selected members of the group consisting of monohydroperoxide of diisopropylbenzene (MHP), isopropylbenzenemononocarbinol (MCL), diisopropylbenzenedicarbinol (DCL), acetylisopropylbenzenemononocarbinol (KCL) and other peroxides organic; b) feed the oxidized product, a solution of soda Caustic and an organic solvent to an Extraction Karr column with caustic soda; c) continuously and simultaneously generate two currents from the Karr column of soda excision of stage b), comprising the first current of Extraction is caustic soda DHP, HHP and KHP extracted in a countercurrent operation, and comprising the second current one or more selected members of the caustic soda group consisting of MHP, MCL, DCL, KCL, other organic peroxides, the organic solvent feed to the Karr column of Extraction with caustic soda and diisopropylbenzene; d) feed continuously the first current of excision with caustic soda of step c), an organic solvent cooled to a temperature between about 10 and 30 ° C and an alkaline solution at a Karr's second column; e) generate continuously and simultaneously two streams from the second column of extraction Karr, the first cold extraction stream comprising a solution organic cold comprising HHP and KHP and comprising the second cold extraction stream enriched caustic soda solution in DHP; f) continuously feed the caustic soda solution enriched with DHP from step e) and an organic solvent that has been heated to a temperature between approximately 40 and 85 ° C at a third column of extraction Karr; g) generate two currents from the third column of extraction Karr, comprising the first stream a hot organic solution comprising High purity DHP and comprising the second solution of soda poor caustic low levels of hydroperoxides not extracted; h) concentrate the organic solution of step g) and feed the concentrated to a continuous dissociation reactor in which dissociates DHP in the presence of an acid catalyst to produce a solution comprising the corresponding dihydroxybenzene and acetone; and i) decompose the HHP present in the organic extract stage e) cold by treatment with an aqueous solution of sodium under non-hydrogenated atmospheric pressure and conditions aqueous to obtain the corresponding dicarbinol.

The process for the production of a phenol dihydroxylated, such as resorcinol or hydroquinone, and dicarbinol of according to the present invention generally involves production of diisopropylbenzene dihydroperoxide (DHP) e diisopropylbenzene hydroxyhydroperoxide (HHP) from diisopropylbenzene (DIPB) and subsequent conversion of DHP into the corresponding dihydroxylated phenol and HHP in dicarbinol correspondent. Preferably, the DIPB used here, and from which is produced by DHP and HHP, is m-diisopropylbenzene (m-DIPB), p-diisopropylbenzene (p-DIPB) or mixtures thereof.

The oxidation of DIPB; such as m-DIPB or p-DIPB, is carried out generally in liquid phase in the presence of a gas containing oxygen, which can be pure oxygen, such as molecular oxygen, or a mixture containing oxygen, such as air. The reaction of oxidation can be carried out in a continuous or discontinuous method, depending on the needs and preferences of the user. Is oxidation reaction can be carried out in the presence or absence of one or more basic catalysts; preferably, a basic catalyst such as sodium hydroxide or sodium carbonate. The presence of these basic substances in the oxidation reaction increases oxidation efficiency, such as improving oxidation rate retarding the development of acidity excessive due to the formation of carboxylic acids, including, but not limited to, formic acid or acetic acid, which prevent oxidation reaction The preferred pH for the oxidation reaction It is in the range of about 7 to 11. The product of DIPB oxidation obtained, for example, by the process of continuous oxidation described in British Patent No. 727,498 or by the discontinuous oxidation process described in the U.S. Patent 4,237,319 is suitable for use in the methods of the present invention; DIPB oxidation methods taught in other patents or publications may also be used, including, but not limited to, the non-alkaline anhydrous procedure taught in US Pat. No. 4,935,551.

The oxidation reaction can be carried out at over a wide range of temperatures, preferably between 80 and 120 ° C. For practical purposes, when the reaction is carried out in the presence of an aqueous solution of caustic soda, the reaction of oxidation is preferably performed at about 90 ° C ± 5 ° C and between 1.38 and 5.52 bar (20-80 psi) of Pressure.

DIPB oxidation results in a oxidized product comprising both the desired DHP and HHP In addition to numerous oxidation byproducts. These byproducts include, for example, hydroperoxides such as monohydroperoxide of isopropylbenzene (MHP) and acetylisopropylbenzene hydroperoxide (KHP); carbinoles such as isopropylbenzenemononocarbinol (MCL) and diisopropylbenzenedicarbinol (DCL); ketones such as acetylisopropylbenzene (MKT) and acetylisopropylbenzenemononocarbinol (KCL); and other organic peroxides formed from the reaction of carbinoles and hydroperoxides, collectively referred to herein "organic peroxides". The formation and accumulation of these by-products in the oxidation reaction not only affects the DIPB oxidation rate but adversely influences the DHP separation of the oxidized product by the methods of extraction carried out later in the procedure.

The oxidized product is then subjected to Extraction with caustic soda. Extraction with caustic soda from according to the present invention is carried out using a column from Karr. As will be appreciated by experts in the specialty, a Karr column is a column that has a deflector system of alternate dishes A solution of caustic soda, the oxidized product and an organic solvent is fed to the Karr column in a "countercurrent" mode. Suitable organic solvents include, but are not limited to, toluene and m-xylene; preferably, the organic solvent is DIPB. The soda solution Caustic predominantly removes DHP while DIPB or other Organic solvent removes impurities. It is a characteristic of the present invention that the complete or almost complete separation of DHP of DIPB oxidation product and removal of impurities oxidation of caustic soda extract are carried out leading to perform caustic soda excision and treatment with DIPB simultaneously in a single Karr column extractor. When perform the excision with caustic soda, the following conditions in the Karr column: the speed of agitation; temperature; and the feed rates of the oxidized product, caustic soda solution and solvent organic. Stirring should be done at a speed that allows that at least one phase of the solution or mixture is dispersed. Preferably, a stirring speed of between 0.83 and 5.0 Hz (50 and 300 strokes per minute), more preferably between approximately 1.67 and 6.67 Hz (100 and 150 paths per minute). Yes stirring speed is too fast, then it will occur overflow in the column resulting in an extraction poor. On the other hand, a slow stirring speed will reduce the mixing between the oxidized product and the caustic soda solution resulting in a poor separation of DHP. The temperature of extraction, that is, the temperature of the solution within the column, is preferably anywhere in the range of about 10 to about 80 ° C. If the temperature is higher than about 80 ° C, then dihydroperoxide tends to decompose in the presence of caustic soda solution giving as result in reduced DHP performance. Column temperatures below approximately 10 ° C avoid proper mixing of the oxidized product and caustic soda solution. For operations ideal, based on intensive extraction tests with the spine of Karr, the temperature is preferably maintained between 25 and 40 ° C. The feed rates of the oxidized product, the solution of caustic soda and organic solvent will vary depending on various factors, such as the amount of oxidized product that is treats and the amount of DHP and HHP present in the oxidized product. The optimization of these feed rates can be determined by an expert in the specialty based on the conditions and user needs.

It has been found, in accordance with this invention, that when this operation is used in Karr columns with the extraction conditions described previously, the corresponding dihydroperoxide can be easily recovered and effectively from the oxidation mixture in the soda solution caustic Since hydroperoxide impurities, such as MHP, MCL, extracted in caustic soda excision are removed predominantly by treatment with organic solvent or the re-extraction, an oxidation recycle that has these impurities It is ready to be fed back to the oxidation reactor. Is Recycling fraction and a caustic DHP fraction can therefore both obtained simultaneously in a single column of Karr. With this improvement, the oxidation and extraction steps of the procedure hydroperoxidation can be easily performed in series for continuous production and extraction of a stream of soda DHP / HHP caustic for use in phenol production dihydroxylated and dicarbinol by the methods of this invention.

Controlling the composition of both the product oxidized as from oxidation recycling before and after Extraction with caustic soda, it can be seen that all or almost all of the KHP and KCL present in the oxidized product they are extracted in the caustic soda solution. These impurities they will affect the final purity of DHP if they are not removed. The present invention provides the removal of these impurities, which is effectively extracted in the extraction with cold MIBK described more forward and therefore a DHP of purity can be obtained very high.

As previously indicated, the two streams resulting from the first extraction or soda Karr column Caustic include recycling, which contains impurities, and a Caustic fraction of DHP, which will also typically contain HHP, KHP and KCL. While recycling is sent back to the reactor Oxidation of DIPB, the caustic fraction of DHP / HHP is cooled to a temperature between about 10 and 30 ° C and a Karr's second column. Preferably, the soda fraction Caustic is fed directly, without delay, to the second column of Karr once the desired temperature is reached. It is done cooling to minimize or prevent the breakdown of hydroperoxide, which can be accelerated by temperatures high.

Although it is preferred to feed the soda fraction caustic directly or "continuously" to the second column of Karr, it will be understood that this feeding does not have to be done directly. To minimize or prevent the breakdown of hydroperoxides, the caustic soda solution that contains these hydroperoxides should be cooled to a temperature as low as possible if the next extraction is not done directly after caustic soda excision.

In addition to the caustic soda solution rich in DHP / HHP from the first column of Karr, also feed the second Karr column an organic solvent such as a ketone, preferably methyl isobutyl ketone (MIBK), and a sodium hydroxide solution. The solvent is used to extract the HHP and other impurities, such as KHP, KCL, MHP or other peroxides organic known to affect the final purity of DHP. The three solutions must be fed to the second column of Karr in a counter current mode. Two currents are obtained after cold MIBK extraction: a caustic fraction of DHP and a fraction of cold MIBK containing HHP, KHP, KCL, MHP and / or others oxidation byproducts. HHP, used for the production of dicarbinol, is therefore obtained directly and continuously at from the cold MIBK extraction of caustic soda extract using the extraction in the second column of Karr.

As with the extraction with the first column of Karr (caustic soda excision), conditions must be maintained appropriate in the second column of Karr, including temperature, stirring speed and feeding speeds. The condition More important is the temperature inside the column. For one effective operation, column temperature, this is the solution temperature inside the column, must be in the range of 10 ° C to 30 ° C, preferably between about 10 ° C and 20 ° C. Due to these temperature ranges, this stage is called the extraction stage with cold MIBK. The term "cold", as used in this context, refers to temperatures between about 10 ° C and 30 ° C. If the temperature is much higher than about 30 ° C, DHP can pass to the layer from MIBK. Colder temperatures of approximately 10 ° C can make difficult to perform the operation since precipitation may occur. The stirring speed in the second column of Karr should be such that at least one phase of the solution is dispersed, and maintained preferably in a range between 1.67 and 6.67 Hz (100 and 400 runs per minute), more preferably at about 4.17 Hz (250 paths per minute). The feed rate of rich caustic soda extract, the MIBK or other organic solvent and the sodium hydroxide solution can be optimized based on the conditions and user needs. The extract analysis of cold MIBK reveals that all or almost all of the KHP, the KCL, the MHP and / or other impurities present in the soda feed Caustic fed to the second column of Karr is extracted completely in the cold MIBK solution.

The resulting caustic soda extract after of the extraction in the second column of Karr contains almost DHP exclusively, with barely detectable amounts of HHP present in the caustic soda solution. The DHP present in the Caustic soda solution is in the form of the disodium salt and may suffer decomposition at elevated temperatures and storage dragged on. As previously indicated, this extract solution Caustic soda is therefore preferably used directly in The next stage to obtain a high purity DHP. As used here, the term "high purity", when used to describe DHP, means DHP that has a purity of 99.7% or higher.

In accordance with the procedure herein invention, high purity DHP can be made by subjecting the Caustic fraction of DHP from cold MIBK extraction at a second extraction with organic solvent, preferably a second extraction with MIBK. This second extraction with MIBK is a extraction with "hot" MIBK, which is performed in one operation in a third column of Karr. "Hot", as used in This context refers to a temperature between 40 and 85 ° C. The MIBK or other organic solvent is heated to a temperature within this interval before feeding on the third column of Karr, along with the caustic fraction of DHP from the extraction with cold MIBK. This extraction with MIKB "hot" it is preferably carried out in a countercurrent manner, where preheated MIBK is preferably passed from the bottom of the column and the caustic soda solution from the side higher. In this way, DHP salt is not exposed to conditions. higher temperatures known to cause decomposition of DHP. Due to the uniform temperature gradient within the column, the transformation of DHP salt into DHP can be achieved easily during extraction.

For effective column operation, it prefer to run the column with the solution inside the column at a temperature between about 40 and 85 ° C. Controlling the working conditions of the third column of Karr, such as temperature, feed rates and stirring speed, a DHP purity of 99.7% can be achieved. It will be appreciated that the higher the purity of the feed of DHP in the dissociation stage, the greater the purity of the dihydroxybenzene obtained. As previously indicated, the temperatures are preferably maintained between about 40 and 80 ° C, more preferably between about 45 and 70 ° C. The MIBK feed rates and caustic soda solution can be optimized based on conditions and needs of the user. The stirring speed is such that at least one phase of the solution or mixture will be dispersed, preferably between 1.67 and 6.67 Hz (100 and 400 strokes per minute), more preferably approximately 4.17 Hz (250 paths per minute).

The cold and hot extraction stages of the present invention provide a DHP stream of very purity Discharge to the dissociation stage. On the other hand, this very high purity DHP stream is produced in a way effective. Both the present methodology and the product obtained are higher than those presented in the specialty, as in the U.S. Patent No. 4,059,637. This patent describes a procedure in which four extractions are used in mixer-settler for the extraction of DHP from a caustic soda solution previously treated with MIBK to remove the HHP and other impurities. Before DHP extraction, the DHP content and HHP content of the soda solution Caustic as a material is 11.3 and 0.5%, respectively, and the DHP: HHP ratio is equal to 95.8: 4.2. In this extraction of multiple phases, a temperature difference was established between adjacent plates fixing a heating device or cooling to each plate, for example, by circulating water hot or cold water through the hood of the extractors. Since each of the four mixers-settlers is an operation individual, the operation of four mixers-settlers requires the use of many pumps, tanks, mixers and motors. In addition, to maintain the temperature of each dish in each mixer-settler, it may be necessary to heating or cooling with water. In spite of the equipment requirements and conditions, the final purity of the DHP material obtained from this operation is very poor; The contents of DHP and HHP in the product are only approximately 4.83% and 0.38%, respectively, in 211 parts of MIBK extract, which corresponds to a ratio of DHP: HHP of 9.28: 7.2. The final relationship is therefore not much superior than the relationship initial. In contrast, the present invention provides a DHP stream in which the DHP content is 99.7% or higher, using a procedure with much less equipment and much less hand of work.

After extraction with hot MIBK, the DHP concentration in the MIBK is typically between approximately 6 and 12% by weight and the amount of water typically between approximately 1 and 3% by weight. Preferably, the solution Hot DHP / MIBK is concentrated before the dissociation stage, since feeding this excretion solution with hot MIBK directly to the dissociation reactor often has effects adverse on the performance of resorcinol or hydroquinone. Further, it is cheaper to use a concentrated DHP solution to maximize the production of resorcinol or hydroquinone in the unit of dissociation. The hot MIBK solution can be concentrated by any means known in the specialty. In a method preferred, the solution is continuously fed to an evaporator of Empty and concentrate. After evaporation, the concentration of DHP in the solution is typically increased to between about 20 and 40% by weight and is preferably approximately 30% by weight. Water content is reduced typically up to about 0.3% by weight. Although this DHP concentration is adequate for feeding dissociation, higher concentrations of DHP Similarly, although a water content of approximately 0.3% by weight does not seem to affect the speed of dissociation, this concentration can be decreased by applying more stringent evaporator conditions.

To effect acid dissociation of DHP contained in the concentrated MIBK solution, a Any of the conventional techniques. In addition, the reaction of dissociation can be carried out by a continuous procedure or discontinuous The reaction can take place within a wide temperature range, for example between about 30 and 100 ° C It has been found convenient to carry out the reaction in the boiling point of the reaction mixture, which is typically in the range of about 60 to 80 ° C depending on the Acetone content in the dissociation reactor. Through this method, the heat of reaction is dissipated through reflux. The DHP dissociation is most conveniently carried out using one or more acid catalysts such as sulfuric acid, trioxide Sulfur, phosphoric acid, hydrochloric acid, boron trifluoride or p-toluenesulfonic acid.

The reactor used in the dissociation operation it may be comprised, for example, of a stirred reactor or a tubular reactor Agitated reactors or reactors backmixing to carry out the dissociation reaction are well known. In accordance with the procedure herein invention, a continuous dissociation reaction is carried out using a stirred reactor. In this type of dissociation operation continuous, the reactor is preferably charged with a mixture of resorcinol or hydroquinone (depending on which dihydroxybenzene is is producing), a sulfur trioxide catalyst dissolved in acetone, and MIBK, and rises to the boiling point of the mixture by heat applied. The incorporation of resorcinol or hydroquinone in the starting load typically improves speed of the dissociation reaction. The DHP / MIBK and trioxide solution sulfur dissolved in acetone is then fed to the reactor at the desired rate and the reaction product is removed continuously at approximately the same speed. In one mode preferred, DHP is fed in the form of a solution in MIBK and Sulfur trioxide is fed into a solution in acetone. Low these conditions, it is possible> 99.5% dissociation of DHP with a residence time in the dissociation reactor between approximately 5 and 10 minutes.

Once DHP has dissociated or transposed to the corresponding dihydroxylated phenol, the product of the dissociation reaction must be neutralized to remove the acid; The dihydroxylated phenol can then be recovered. The recovery of a polyhydroxylated phenol, such as resorcinol or hydroquinone, of the dissociation reaction mixture by, by example, distillation, extraction and crystallization, is described in the technique. In accordance with the process of the present invention, the resorcinol yield of the dissociation reaction is between approximately 94 and 95% and the purity of resorcinol after distillation is approximately 99.7% or greater.

Successful and effective separation of DHP and HHP of the caustic soda solution by extracting with MIBK hot and cold in Karr column continuous gives the raw material of HHP for the production of dicarbinol (DCL). The DCL is used in the manufacture of various organic materials and polymers for various applications

The present invention provides that a aqueous procedure can be used effectively for the conversion of HHP in DCL. This method takes the HHP obtained from the extraction with Cold MIBK and remove the MIBK from the reaction mixture. The mixture is It is then refluxed in an alkaline aqueous solution. The elimination of MIBK, previously not presented in the literature, allows an alkaline aqueous solution to be used effectively for HHP to DCL conversion. The alkaline aqueous solution is preferably an aqueous sodium hydroxide or an aqueous solution of sodium sulphite Using this methodology, the complete decomposition of HHP in reaction times relatively short, such as 1 or 2 hours.

Aqueous solutions of sodium hydroxide and Sodium sulphite not only breaks down HHP to DCL but also It is also believed to break down the other hydroperoxides, namely KHP and MHP, in their corresponding carbinoles (KCL and MCL) although the Inventors do not want to limit themselves by this. In the case of decomposition with sodium sulphite, according to the procedure of the present invention, the conversion of HHP into DCL can achieved even in the presence of MIBK solvent. After the decomposition, the DCL product is filtered and purified to Continuation easily for commercial markets. The process of the present invention therefore provides a Improved and safe aqueous procedure for the manufacture of DCL a from HHP material.

The organic solvent used in the extractions "cold" and "hot" in the columns of Karr second and Third can be recycled and reused. This organic solvent, which is preferably MIBK, can be recovered from the current of HHP generated during extraction with cold MIBK before the stage of decomposition. The MIBK can be recovered, for example, through of the distillation of the HHP stream. Similarly, the MIBK residual in the poor caustic soda solution can be recovered to through distillation of the poor caustic soda stream generated during "hot" extraction in the third column from Karr. MIBK, or other organic solvent, recovered, can then recycle to the extraction stages in the columns of Karr second and third. This recycling contributes additionally to the economy and effectiveness of the present methods.

It will be appreciated that the present invention provides a means for the preparation of DHP and HHP using Karr columns. These columns of alternative dishes of Karr they have several advantages over known methods to obtain a fraction of pure DHP, namely: high efficiency and high are achieved capacity (high volumetric efficiency) in a simple compact unit; and the elimination of the many pumps, mixers and required engines, for example through operations of mixer-settler. Only one is required Karr column for each of the three extraction stages, in opposition to the multiple mixers and settlers required in the methodologies presented in the specialty. The ability to easily invert phases during extraction is another advantage of The present methods. Experimental work showed that when the aqueous phase enriched in DHP was dispersed in the columns of Marr Karr both "cold" and "hot", the coalescence at the interface it was good and the implication of the solvents was insignificant.

In Karr's single-column operations of the present invention, the temperature of the aqueous alkali layer is gradually increases as the layer is passed in a countercurrent mode across the plates. Therefore, the Karr column operation avoids a temperature difference large or uneven between adjacent plates and a uniform temperature gradient from the bottom to the top of the column.

Preferably, the three Karr columns used in the present methods they are connected and work in series. So, the present invention provides an advantage over the specialty since any or all of the stages described here can be carried out continuously, sending the product from a column directly, or without noticeable delay, to the column next. The ability to effect such an effective continuous method does not He has previously presented in the specialty.

The columns for extracting alternative dishes of Karr that are used in the present invention can be obtained from KOCH Process Technology, 1055 Parsippany Blvd., Parsippany, NJ 07054.

NMR spectroscopy was used to characterize the oxidation products of the starting DIPB solution using the proton magnetic resonance (PMR) method. The present invention therefore also addresses a method for use PMR to determine the composition of the various streams generated by the methods of the present invention. Besides of raw oxidation product (oxidized product), were developed PMR methods to characterize the recycled product, the Extraction products with hot and cold MIBK, feeding dissociation and the dissociation product, and the product obtained in different distillation phases in resorcinol recovery from high purity The use of the PMR technique allowed characterization of all the components of the hydroperoxidation process of DIPB including organic peroxides, which were not previously They identified. This characterization was not previously presented in the specialty.

\hbox{orgánicas son:}

For the qualitative characterization of the various currents described previously, a PMR analysis was performed. The PMR analysis according to the present invention uses the five most common organic residues produced from the oxidation of DIPB to identify the compounds present in each stream; these structures

 \ hbox {organic are:} 

aril-C - (= O) -CH_ {3} aryl-C- (CH 3) 2 -OOH aryl-C- (CH 3) 2 -OH aril-CH (CH 3) aril-C (CH 3) = CH2

The portion of the structure shown in bold represents the hydrogens (protons) that were actually used to determine the structures present in each stream or product. PMR spectra were obtained for the oxidized product, the recycle streams and excretion streams with cold MIBK hot. The identification of each peak of each spectrum is determined by comparing the positions of the peaks with those obtained using patterns for each component of the currents.

To determine the molar ratio of components in each stream or product, the value of the integral for the structure that was measured. Measuring the height of the integral for each peak and dividing the height by the number of protons that give rise to that integral, the fraction is determined molar of each compound. The number of protons that give rise to the integral or the peak will be 3, 6 or 12, as shown in the formulas of previous organic structures and as is known by experts in the specialty. The organic composition of these streams is found below by a method of "Relationship in Weight "by which the weight fraction of each component, and the total is normalized to equal to 100. Typically, the weight ratio will be very close to the percentage values by weight, as long as the sample does not have a high content of water, inorganic material or compounds that do not contain hydrogen. PMR methods to analyze the dissociation product and the distillation samples differed, since there are unassigned compounds or unknown in these products that cannot be measured or compared against known patterns. A method of "Internal Pattern / PMR" can be used to analyze these currents, in which a portion Sample weighing is "seasoned" with a known amount of a organic compound or "internal standard". Any can be used organic compound, provided there are no problems with the compatibility. Methylene chloride is preferred for this use, which is compatible with the products and which gives only 1 peak in the spectrum. When methylene chloride is used, they should be used between approximately 20 and 30 mg per 100 mg of sample. The weight of each analyte is found below according to the following formula:

\ analyte weight = (weight \ of \ compound \ organic) \ (N_ {s} / N_ {a}) (M_ {a} / M_ {s}) (A_ {a} / A_ {s})

where

N_ {s} = number of protons of the internal standard (2 for methylene chloride)

N_ {a} = number of protons in the analyte for measured structure

M_ {s} = molecular weight of the standard (85 for methylene chloride)

M_ {a} = molecular weight of the analyte

A_ {s} = area of the pattern integral

A_ {a} = area of the analyte integral.

The weight of the analyte is divided by the weight of the sample to give the percentage by weight of each analyte in the total composition

Before performing the PMR analysis on the Caustic soda streams rich in DHP / HHP and DHP from the Extraction Karr column with caustic soda and Karr column Extraction with cold MIBK, the currents must undergo a Extraction to remove NaOH. Extraction is done using a organic solvent, such as benzene. For example, a quantity known of the current should be treated with dry ice to carry the current up to a pH within the range of about 9 and 9.5 and extracted with benzene. The sample can be tested at continuation or can be further treated by separating distillation of benzene and the remaining residue analyzed by PMR methods. Other streams and products can be analyzed directly.

The 200 MHz PMR spectra can be acquired, for example, with a Varian Gemini 200 spectrometer FT-NMR, commercially available from Varian Associates, Palo Alto, CA, preparing 3 to 5% (by weight) of what unknown in acetone-d6 ((CD 3) 2 C = O). Typical acquisition parameters are as follows: width of pulse = 8 microseconds (a pulse of 30 degrees); delay pulse = 3 seconds; acquisition time = 4 seconds; the number of transitions = 100. The spectra are "divided" into sections 0.3 ppm (60 Hz) wide with full integration for each and measurement accuracy Parameters other than these can be optimized based on the needs and apparatus of the user. It will be appreciated that the spectra can be isolated to more than 200 MHz, depending on the needs and equipment of the user. The spectra obtained using less than 200 MHz will typically have a resolution inadequate

The PMR analysis method offers advantages on other analytical techniques for the analysis of materials of hydroperoxidation, namely: the technique is not destructive; all samples are analyzed in deuterated solvents that provide a internal reference to ensure chemical displacement values correct; the technique is based on measures of integrals that arise from the different types of protons present in the mixture - since all protons organically bound to a carbon atom "will respond" in an equivalent manner, there is no need to determine a "response factor" for each compound; everybody components are measured from a single spectrum (changes in the instrumental conditions they will not affect the analysis); one time that the chemical shift values have been determined for a pattern, there is no need to simultaneously analyze the pattern during the analysis of unknown mixtures; and the analysis is fast, typically requiring 15 minutes or less of time instrumental.

As an aid to understand the procedure of the present invention, the simultaneous extraction of DHP and HHP from oxidized product and its subsequent separations by hot and cold MIBK extractions using column operations of Karr are described with reference to the schematic flow chart illustrated in figure 1, knowing that this is a modality Exemplary of the present invention. Referring to figure 1, three Karr columns are connected in series and are called Column of Extraction Karr with Caustic Soda 2, Extraction Karr Column with Cold MIBK 4 and Extraction Karr Column with Hot MIBK 6. The oxidation of the oxidation material 8 of DIPB or oxidized product which comes from DIPB Oxidation Reactor 10, the washing DIPB and 8% aqueous sodium hydroxide are fed to Column 2 of Karr Extraction with Caustic Soda so that the DIPB and the solution of caustic soda flow countercurrently in the column of Extraction with caustic soda. The recycled 12 organic ("recycled of oxidation ") collected from the column will be returned directly to DIPB Oxidation Reactor 10 for further oxidation. The aqueous caustic soda solution enriched with DHP and HHP ("DHP / HHP-rich caustic soda solution") 14 separate by means of Column 2 of Karr of Extraction with Caustic Soda sends to Column 4 of Karr of Extraction with Cold MIBK after Cool through a cooler (not shown). In Column 4 of Karr Extraction with Cold MIBK, the caustic soda solution 14 rich in DHP / HHP, a solvent of MIBK and hydroxide solution 8% sodium are introduced in such a way that both the MIBK and the Caustic wash soda solution are passed between each other in countercurrent in the column. From this column, the solution of MIBK containing HHP is recovered ("Cold MIBK Extract") 16 and the HHP becomes DCL 18 through the use of a solution aqueous sodium sulphite or sodium hydroxide; during this conversion, the MIBK solvent is also recovered for recycling (not shown). The aqueous caustic soda extract enriched with DHP ("Solution of Caustic Soda Rich in DHP") 20 separates from Column 4 of Karr Extraction with Cold MIBK and pumped directly to Column 6 of Karr of Extraction with Hot MIBK. In this column, the Caustic Soda Solution Rich in DHP 20 and MIBK previously heated are pumped so that both the solution of caustic soda as the MIBK solvent are passed between in countercurrent. MIBK Hot Extract 22 obtained from this Extraction contains DHP with a purity above 99.7%. The HHP impurity present in this DHP material is typically 0.3%; The weight ratio of DHP / HHP in the MIBK extract is by therefore approximately 99.7: 0.3. MIBK Hot Extract 22 is subsequently concentrated (not shown) and dissociates into presence of an acid catalyst to produce the phenol dihydroxylated, such as resorcinol, and acetone 24. The solution of Caustic soda 26 poor collection of Column 6 of Karr de Extraction with hot MIBK can be recycled after separating by drag the dissolved MIBK.

Examples

The present invention is further described. in more detail by means of the following Examples. All parts, percentages and ratios are by weight.

Example 1 Preparation of diisopropylbenzene oxidation mixture

300 parts of m-diisopropylbenzene (m-DIPB) with 30 parts of m-diisopropylbenzene monohydroperoxide (MHP; initiator) and 10 parts of 4% aqueous sodium hydroxide (catalyst) in a 1 liter Parr reactor and oxidize making pass air at the speed of 20 liters / hour with good agitation. The temperature of the oxidation reaction mixture was maintained at approximately 90 ° C. The oxidation was continued until the product contained 70 to 75% hydroperoxide (determined by iodimetric titration and calculated as monohydroperoxide of diisopropylbenzene). The NMR analysis of this material from oxidation (oxidized product) showed the presence of approximately 15-18% dihydroperoxide m-diisopropylbenzene (DHP) and 3 to 5% of m-diisopropylbenzene hydroxyhydroperoxide (HHP) in addition to the oxidation by-products shown in Table 1, more forward, and DIPB without reacting.

Continuous and simultaneous separation of DHP and HHP from the product of m-DIPB oxidation

The oxidized product obtained from the oxidation of m-DIPB was cooled to room temperature and was pumped a Karr Column (Extraction Column with Sosa Caustic) at a speed of 100 parts / hour. Separately, it pumped m-diisopropylbenzene and sodium hydroxide 8% aqueous to the column at the rate of 13.5% parts / hour and 88.8 parts / hour, respectively, such that both liquids passed countercurrent in the column. During this operation, the column temperature was maintained between 25 and 40 ° C and separated continuously two phases, namely organic and aqueous. The organic phase it was collected at the speed of 91.8 parts / hour and contained the majority of monohydroperoxide (MHP) as well as oxidation products not extracted by the caustic solution. This recyclable organic phase can be effectively returned to the oxidant for continuous oxidation or discontinuous The aqueous phase (rich caustic soda extract) enriched with DHP, HHP, KHP and other removable impurities with Caustic soda solution was collected at the speed of 110.5 parts / hour.

The rich caustic soda extract obtained from the Karr's first column (caustic soda extraction) cooled and Karr's second column (cold MIBK column) was pumped to a speed of 110.5 parts / hour; the column temperature of the second column was maintained between approximately 10 and 30 ° C of temperature during extraction. The methyl isobutyl ketone and solutions Aqueous 8% sodium hydroxide was pumped respectively to the column at the speed of 58.5 parts / hour and 51.0 parts / hour. When these two solutions were passed in countercurrent in the column, HHP, KHP and all oxidation impurities present in the caustic solution they were extracted in the organic phase. The phase Organic enriched in HHP (cold MIBK extract) was collected at 63.5 parts / hour speed. It was found that soda extract aqueous caustic separated from this Karr column operation It contained 99.8% DHP.

Without isolation or recovery, the extract of DHP-rich caustic soda obtained from the cold MIBK column is pumped directly to a third column of Karr (column of MIBK hot). Separately, solvent of methyl isobutyl ketone previously heated was pumped to this column at a speed of 134.5 parts / hour such that this solvent passed in countercurrent with the caustic soda solution. A uniform temperature gradient across the column so that the column temperature was between about 30 and 70 ° C. The DHP present in the caustic soda solution was extracted effectively with minimal decomposition and MIBK extract (hot MIBK extract) was collected at a rate of 151.1 parts / hour. It was determined that the purity of DHP obtained from This extract was 99.7%. The aqueous solution of caustic soda (poor caustic soda solution) recovered at the speed of 139.5 parts / hour of this column can be recycled back to the column Extraction with caustic soda after the withdrawal of MIBK dragged

Table 1 summarizes the compositions of different currents according to the methods of Example 1.

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TABLE 1

one

The hot MIBK extract obtained from the Karr's third column was concentrated to 30% by weight of DHP. During this concentration, the water content of the solution of DHP / MIBK was reduced from 3.0% by weight to 0.3% by weight. East material was used in the following decoupling operation keep going.

Continuous dissociation of DHP material

To a glass reactor equipped with a stirrer mechanical, a thermometer, a reflux condenser and a device overflow was charged and heated to reflux a solution that it contained resorcinol, methyl isobutyl ketone and 0.06 parts by weight of SO 3 dissolved in acetone solution with the ratio by weight of 8:52:40. Solutions containing 30% weight / weight of DHP in methyl isobutyl ketone (solution from the hot MIBK extract) and 0.06% weight / weight of sulfur trioxide in dried acetone was fed to the reactor at a speed of 50.0 parts / hour and 26.9 parts / hour, respectively, such that the total residence time was 10 minutes. The Dissociation reactor content temperature was maintained at the boiling point. The reactor dissociation product overflowed with a collector in which the acid catalyst neutralized immediately and continuously. The product collected, after steady state conditions, it gave a 94% yield of resorcinol based on feeding DHP

Manufacture of DCL from HHP (sulfite decomposition sodium with an azeotropic distillation method)

The cold MIBK extract obtained from Karr's second column up to about 40% by weight of HHP material in the MIBK. By doing this operation, most of the MIBK solvent can be recovered and recycled effectively.

The reactor, equipped with a mechanical stirrer, a Dean-Stark thermometer and a condenser, was charged with 100 parts of 40% HHP in methyl isobutyl ketone (extract of Cold MIBK containing 77.8% HHP) and 140 parts aqueous solution of 20% sodium sulphite. The reactor contents were heated to reflux and all the MIBK solvent present in the reactor was removed completely by azeotropic distillation. After the solvent removal, the reactor content was subjected to reflux for a period of 2.0 hours and cooled to precipitate the DCL. The white precipitate separated from the aqueous solution is filtered, washed with water and then dried. Performance it was 26.7 parts with a purity of 94.2%. From the results From this experiment, all the HHP present in the MIBK extract cold broke down completely until DCL.

From this example, it is evident that both Resorcinol such as dicarbinol may occur simultaneously at from diisopropylbenzene.

Example 2

In this example, the two methods are described developed for the decomposition of HHP to DCL through the aqueous sodium sulphite solution.

An extract of cold MIBK obtained from the column of Karr was concentrated to about 40% by weight of material of HHP and was used in the following two experiments:

Decomposition of HHP to DCL by sodium sulphite aqueous A. Azeotrope method

They were added to an equipped three-mouth flask with a mechanical stirrer, a thermometer and a condenser of Dean-Stark 100 parts of HHP / MIBK and 140 parts of 20% aqueous solution of sodium sulphite. Then the flask contents were heated and brought to reflux. During this period of reflux, by means of separation of Dean-Stark, all the MIBK solvent present in The solution was removed. After this, the contents of the flask are refluxed for an additional period of 2.0 hours and at then cooled. The solid material separated during the cooling was filtered, washed with water, dried and analyzed with regarding its decomposition through NMR analysis. The yield was 28.4 parts with 94.2% purity. The results are summary in Table 2, below.

B. Reflux Method

They were added to a three-mouth flask with a mechanical stirrer, a thermometer and a reflux condenser 100 parts of HHP / MIBK concentrated solution and 140 parts of sulphite 20% aqueous sodium. The contents of the flask were heated and carried until reflux for 2.0 hours. After this reflux, the mixture The reaction was cooled and the separated white precipitate was filtered, washed with water, dried and analyzed by NMR with respect to its composition. The yield was 21.6 parts and the purity was 97.6%. The results of this experiment are summarized in Table 2.

TABLE 2

two

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When analyzing the results of Table 2, note that the decomposition of HHP using an aqueous solution of sodium sulfite can be used successfully for conversion Safe and effective HHP in DCL. Through this method, it was observed that HHP material became completely corresponding carbinol under atmospheric conditions. With this method, even before purification, the DCL obtained was of high purity.

Example 3

In this example, procedures are described for make DCL directly from the cold MIBK extract using aqueous solution of sodium hydroxide.

Experiment No. one

They were added to an equipped three-mouth flask with a mechanical stirrer, a thermometer and a reflux condenser 100 parts of cold MIBK extract, obtained from the operation with Karr column, and 24 parts of aqueous caustic soda solution at 4%, and they were refluxed for a period of 5.0 hours. After this period of reflux, the solution was cooled and the both aqueous and organic layers were separated and the organic layer was analyzed with respect to its composition by NMR analysis. To the analyze the results, it was observed that the concentration of HHP in the MIBK layer remained unchanged indicating that it was not HHP decomposition taking place under conditions previous.

Experiment No. two

Experiment No. 1 was repeated using solution 8% aqueous sodium hydroxide instead of aqueous solution of 4% sodium hydroxide. The MIBK phase separated after the period Reflux was analyzed by NMR with respect to its composition. From Again, no change in HHP concentration was observed. The results obtained from Experiments 1 and 2 are summarized in Table 3, below.

In investigating this further, it was discovered that the decomposition of HHP could be completed effectively removing MIBK from the reaction mixture before refluxing. With this discovery, a method to decompose was developed effectively HHP up to DCL. Therefore, using the method described in Experiment No. 3, DCL could be manufactured safely and economical The advantages of this method are that it is aqueous, it is performed under atmospheric pressure conditions instead of non-high pressure and It is done without the use of hydrogen.

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TABLE 3

3

Experiment No. 3

They were added to an equipped three-mouth flask with a mechanical stirrer, a thermometer and a condenser of Dean-Stark 100 parts of concentrated HHP / MIBK and 44.4 20% aqueous sodium hydroxide parts. The contents of the flask are heated and underwent reflux. During this period of reflux Initial, all of the MIBK solvent was completely removed as a azeotrope After this, the reactor contents were subjected to reflux for an additional period of 1.0 hours. Then, the solution was cooled and the separated white precipitate was filtered, washed with distilled water, dried and analyzed by NMR with Regarding its composition. The yield was 26.4 parts with a 94.6% purity. The results of this experiment are summarized in the Table 4 and clearly suggest that it can also be used effectively an aqueous solution of sodium hydroxide for decomposition full of HHP.

(Table goes to page next)

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TABLE 4

4

Example 4 Preparation of the diisopropylbenzene oxidation mixture

A Parr reactor was loaded with 100 parts of m-diisopropylbenzene (m-DIPB), 10 oxidation recycling parts (initiator) and 2 solution parts of 5% sodium carbonate (catalyst). The previous mixture was heated to 95 ° C and oxidized by passing a fine stream of air to the solution agitated quickly. The oxidation was continued until the oxidation mixture in the reactor contained 75% by weight of hydroperoxide (calculated as monohydroperoxide of diisopropylbenzene by iodimetric titration). The result of the analysis of this m-DIPB oxidation material (oxidized product) is given in Table 5, below.

Continuous and simultaneous separation of DHP and HHP from a product of m-DIPB oxidation

The oxidized product obtained from the oxidation of m-DIPB was cooled to room temperature and was pumped to a column of Karr (Sosa Extraction Column Caustic) at a speed of 100 parts / hour. Separately, it pumped m-diisopropylbenzene and sodium hydroxide 8% aqueous to the column at the speed of 12.9 parts / hour and 73.6 parts / hour, respectively, such that both liquids passed countercurrent through the column. During this operation, the column temperature was maintained between 25 and 40 ° C and separated continuously two phases, namely organic and aqueous. The organic phase it was collected at the speed of 93.5 parts / hour and contained the majority of monohydroperoxide (MHP) as well as oxidation products not Removable by caustic solution. This organic phase recyclable can be effectively returned to the oxidizer for continuous or discontinuous oxidation. The aqueous phase (soda extract rich caustic) enriched with DHP, HHP, KHP and other impurities Extractables with caustic soda solution shown in Table 5 are picked up at the speed of 91.0 parts / hour.

The rich caustic soda extract obtained from the Karr's first column was cooled and pumped to the second column from Karr (cold MIBK column) at a speed of 91.0 parts / hour; this column temperature was maintained between about 10 and 30 ° C temperature during extraction. The methyl isobutyl ketone and solutions Aqueous 8% sodium hydroxide was pumped respectively to the column at the speed of 63.4 parts / hour and 52.0 parts / hour. When these two solutions were passed in countercurrent in the column, HHP, KHP and all oxidation impurities present in the caustic soda solution they were extracted in the organic phase. The Organic phase enriched in HHP (cold MIBK extract) was collected at the speed of 68.6 parts / hour. It was found that the extract of aqueous caustic soda separated from this Karr column operation It contained 99.8% DHP.

Without isolation or recovery, the extract of DHP-rich caustic soda obtained from the cold MIBK column is pumped directly to a third column of Karr (column of MIBK hot). Separately, solvent of methyl isobutyl ketone previously heated was pumped to this column at a speed of 138.0 parts / hour such that this solvent passed in countercurrent with the caustic soda solution. A uniform temperature gradient across the column so that the column temperature was between about 30 and 70 ° C. The DHP present in the caustic soda solution was extracted effectively with minimal decomposition and MIBK extract (hot MIBK extract) was collected at a rate of 150.0 parts / hour. It was determined that the purity of DHP obtained from this Extract was 99.7%. The aqueous solution of caustic soda (solution of poor caustic soda) recovered at the speed of 127.6 parts / hour of this column can be recycled back to the extraction column with caustic soda after removal of dragged MIBK.

Table 5 summarizes the results of the experiment. previous.

TABLE 5

5

The hot MIBK extract obtained from the Karr's third column was concentrated to 24.8% by weight of DHP. During this concentration, the water content of the solution of DHP / MIBK was reduced from 3.0% by weight to 0.3% by weight. East material was used in the following decoupling operation keep going.

Continuous dissociation of DHP material

To a glass reactor equipped with a stirrer mechanical, a thermometer, a reflux condenser and a device overflow was charged and heated to reflux a solution that it contained resorcinol, methyl isobutyl ketone and 0.06 parts by weight of SO 3 dissolved in acetone solution with the ratio by weight of 8:52:40. Solutions containing 24.8% weight / weight of DHP in methyl isobutyl ketone (solution of the hot MIBK extract) and 0.06% weight / weight of trioxide Sulfur in dried acetone was fed to the reactor at a rate of 100.0 parts / hour and 53.8 parts / hour, respectively, thereby that the total residence time was approximately 5 minutes. The Dissociation reactor content temperature was maintained at the boiling point. The reactor dissociation product overflowing the collector in which the acid catalyst was neutralized immediately and continuously. The product collected, after steady state conditions, gave a yield of 91% of Resorcinol based on DHP feeding.

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Manufacture of DCL from HHP (decomposition with hydroxide sodium with the azeotropic distillation method)

The cold MIBK extract obtained from the second Karr column was concentrated to obtain 40% by weight of material from HHP in the MIBK. Performing this operation, most of the solvent MIBK can be recovered and recycled effectively.

A reactor equipped with a mechanical stirrer, a Dean-Stark thermometer and a condenser, was charged with 100 parts of 40% HHP in methyl isobutyl ketone (extract of Cold MIBK containing 76.2% of HHP) and 44.4 parts of solution 20% aqueous sodium hydroxide. The reactor contents are heated to reflux and all the MIBK solvent present in the reactor was completely removed by azeotropic distillation. After removal of the solvent, the content of the reactor is refluxed for a period of approximately 1.0 hours and cooled to precipitate the DCL. The white precipitate separated from The aqueous solution was filtered, washed with water and then dry. The yield was 26.2 parts with a purity of 97.1%. TO from the results of this experiment, it was determined that everything the HHP present in the cold MIBK extract was decomposing completely.

From this example, it is clear that they can both resorcinol and dicarbinol be produced from diisopropylbenzene.

Example 5

A Parr reactor loaded with 330.0 parts of p-diisopropylbenzene, 10.0 parts recycled from oxidation and 9.0 parts of 4% aqueous sodium hydroxide was heated up to 95 ° C. The oxidation of the previous mixture was started by pass a fine stream of air at a speed of 20 liters / hour in a rapidly stirred solution. Oxidation reaction It took approximately 14.0 hours to reach 75% content of hydroperoxide calculated as diisopropylbenzene monohydroperoxide by iodimetric evaluation. This oxidation material of p-DIPB could also be used to make the corresponding dihydroxylated phenol, namely hydroquinone, and dicarbinol by the process of this invention.

Claims (25)

1. A method of manufacturing dihydroxybenzene and dicarbinol from diisopropylbenzene, comprising: a) oxidize diisopropylbenzene (DIPB) in the presence of a basic catalyst to obtain an oxidized product that comprises diisopropylbenzene dihydroperoxide (DHP), diisopropylbenzene hydroxyhydroperoxide (HHP), hydroperoxide acetylisopropylbenzene (KHP) and one or more selected members of the group consisting of diisopropylbenzene monohydroperoxide (MHP), isopropylbenzenemononocarbinol (MCL), diisopropylbenzenedicarbonate (DCL), acetylisopropylbenzenemononocarbinol (KCL) and other peroxides organic; b) feed the oxidized product from step a), a solution of caustic soda and an organic solvent to a first Karr's column; c) generate two currents from the first Karr column of stage b), comprising the first stream Extraction with DHP, HHP and KHP caustic soda extracted in a countercurrent operation, and comprising the second current one or more selected members of the caustic soda group consisting of MHP, MCL, DCL, KCL, other organic peroxides, DIPB and the organic solvent of step b); d) feed the first excretion current with caustic soda from step c), a cooled organic solvent up to a temperature between 10 and 30 ° C and an alkaline solution at a second column of Karr; e) generate two currents from the second Karr column, comprising the first extraction current cold a cold organic solvent extract comprising HHP and KHP and comprising the second bland cold extraction stream DHP-enriched caustic; f) feed an organic solvent having a temperature between 40 and 85ºC and the caustic soda enriched in DHP from stage e) to a third column of Karr; g) generate two currents from the third Karr column, comprising the first extraction current heat a solution in hot organic solvent comprising High purity DHP, and comprising the second current of hot extraction poor caustic soda that has low levels of hydroperoxides not extracted; h) concentrate the solution in organic solvent heat from stage g) and feed the concentrate to a reactor of continuous dissociation in which DHP dissociates in the presence of a acid catalyst to produce a solution comprising the corresponding dihydroxybenzene and acetone; and i) decompose the HHP present in the first cold extraction current from stage e) by treatment with an aqueous alkaline solution under atmospheric pressure and conditions aqueous to obtain the corresponding dicarbinol. 2. The method according to claim 1, in which at least two successive stages are continuously performed selected from the group consisting of any of the stages a) to g). 3. The method according to claim 1, wherein the oxidation of diisopropylbenzene is performed using molecular oxygen 4. The method according to claim 3, in which the oxidation stage is performed using a continuous method or discontinuous 5. The method according to claim 1, which includes performing said oxidation stage at a temperature between 80 and 120ºC and a pressure between 1.38 and 5.52 bar (20 and 80 psi) and use an alkaline solution as the basic catalyst selected from the group consisting of sodium carbonate and hydroxide sodium 6. The method according to claim 1, wherein the organic solvent of step b) is DIPB. 7. The method according to claim 1, which also includes the stage of recycling the second stream of Extraction with caustic soda produced in stage c) to the stage of oxidation of stage a). 8. The method according to claim 1, wherein the organic solvent used in step d) and step f) It is methyl isobutyl ketone (MIBK). 9. The method according to claim 1, in which the temperature of the solution within the second column de Karr is between 10 and 30ºC. 10. The method according to claim 1, in which the temperature of the solution in the third column of Karr is between 40 and 85 ° C. 11. The method according to claim 1, in which the first caustic soda excretion stream of the stage c) feeds directly to the cold extraction of the stage d), and in which the second cold extraction current of the stage e) feeds directly to the hot extraction of the stage F). 12. The method according to claim 1, which includes carrying out the concentration of stage h) by feeding the hot organic solvent solution to an evaporator empty. 13. The method according to claim 1, in which the temperature of the solution inside the reactor of dissociation in step h) is between 60 and 80 ° C. 14. The method according to claim 13, in which the decomposition stage i) is performed at a temperature between 90 and 105 ° C. 15. The method according to claim 1, wherein said first column of Karr, said second column of Karr and said third column of Karr are made to work in series. 16. The method according to claim 1, wherein the alkaline aqueous solution of step i) is selected from the group consisting of an aqueous solution of sodium sulphite and an aqueous solution of sodium hydroxide. 17. The method according to claim 15, in which the stirring speed in the first column of Karr is between 0.83 and 5.0 Hz (50 and 300 runs per minute), the stirring speed in the second column of Karr is between 1.67 and 6.67 Hz (100 and 400 paths per minute) and the speed of agitation in the third column of Karr is between 1.67 and 6.67 Hz (100 and 400 routes per minute). 18. The method according to claim 1, wherein the acid catalyst of step h) is one or more members selected from the group consisting of sulfuric acid, trioxide sulfur, phosphoric acid, hydrochloric acid, boron trifluoride and p-toluenesulfonic acid. 19. The method according to claim 18, in which the acid catalyst is sulfur trioxide. 20. The method according to claim 8, which also includes the steps of recovering MIBK from the current of poor caustic soda generated in stage g) and the current of decomposition of stage i) for recycling. 21. The method according to claim 1, in which the organic solvent in the first stream of cold extraction is removed before the decomposition stage of the stage i). 22. The method according to claim 1, which also includes the step of determining the composition of one or more streams selected from the group consisting of the product oxidized, the first caustic soda excretion stream, the second current of excision with caustic soda, the first cold extraction current, the second extraction current cold, the first hot extraction current, the second hot extraction current and the dissociation product of the step h) using PMR analysis. 23. The method according to claim 22, in which the current being analyzed is selected from the group consisting of the oxidized product, the first stream of Extraction with caustic soda, the second current of exraction with caustic soda, the first cold extraction stream, the second cold extraction current, the first extraction current hot and the second hot extraction current and analysis by PMR includes: a) obtain a PMR spectrum for a stream; b) determine the integral of a peak that represents each compound in the stream in the PMR spectrum; c) divide the integral of each peak by the number of hydrogens that give rise to each peak to obtain the fraction molar for each compound in the stream; Y d) repeat steps a) to c) for each stream That is analyzed. 24. The method according to claim 23, in which the current being analyzed is selected from the group which consists of the first caustic soda excretion stream and the second caustic soda excretion stream, and includes also the step of extracting the caustic soda solution from the current before performing the PMR analysis. 25. The method according to claim 22, in which the current analyzed is the product of dissociation and analysis by PMR includes: a) add an internal standard to the product of dissociation; b) obtain a PMR spectrum for the mixture of dissociation product / methylene chloride; c) determine the weight of each analyte in the dissociation product according to the formula: \ analyte weight = (weight \ of \ internal \ pattern) \ (N_ {s} / N_ {a}) (M_ {a} / M_ {s}) (A_ {a} / A_ {s}) where N_ {s} = number of protons of the internal standard (2 for methylene chloride) N_ {a} = number of protons in the analyte for measured structure M_ {s} = molecular weight of the standard (85 for methylene chloride) M_ {a} = molecular weight of the analyte A_ {s} = area of the pattern integral A_ {a} = area of the analyte integral.